Process for preparing 1,1,1-trifluoro-2,2-dichloroethane

ABSTRACT

The invention relates to a process for preparing 1,1,1-trifluoro-2,2-dichloroethane (F123). 
     This process consists in placing 1,1,1-trifluoro-2-chloroethane (F133 a ) in contact with chlorine in the presence of hydrogen fluoride and a fluorination catalyst. 
     F133 a  may be obtained by fluorination of trichloroethylene, and the F123 may be subsequently fluorinated to F125.

FIELD OF THE INVENTION

The present invention relates to a process for preparing1,1,1-trifluoro-2,2-dichloroethane (F123) by catalytic chlorination of1,1,1-trifluoro-2-chloroethane (F133a) in the presence of hydrogenfluoride (HF). The invention also relates to the application of thisprocess to a process for manufacturing pentafluoroethane (F125).

BACKGROUND OF THE INVENTION

Since the compounds F123 and F125 may be used as substitutes forperchlorofluorocarbons (CFCs) in the field of aerosols (propellants) andin the field of refrigeration, efficient processes for their industrialproduction are currently being sought.

WO 95/16654 describes the placing in contact, at a temperature of 340°C., of F133a with chlorine and HF in the presence of a chromiumcatalyst. Although the conversion of the F133a in this reaction is high,it mainly produces 1,1,1,2-tetrafluoroethane (F134a) at thistemperature. Thus, the selectivity towards F123 does not exceed 15%,which does not allow a production of this compound under industriallyacceptable conditions to be envisaged.

WO 94/11327 mentions the placing in contact, at temperatures below 300°C., of F133a with chlorine and HF in the presence of a chromiumcatalyst. This reaction is carried out with a very large excess ofchlorine and HF, and preferentially leads to the formation of F124 andF125; thus, the selectivity towards F123 remains less than 8% and the110 series/120 series ratio is greater than 10%.

EP-A-526 908 and EP-A-346 612 propose the preparation of F123 by placingchlorine in contact with F133a, at a temperature preferably between 350and 450° C., in the presence or absence of a catalyst, this chlorinationbeing carried out in the absence of HF.

U.S. Pat. No. 4,145,368 proposes a process that consists in reactingchlorine with F133a, then separating the F123 from the reaction medium,and reacting the F113a resulting from this separation with a furtheramount of F133a, this reaction being carried out in the vapour phase andpreferably between 350 and 425° C., in the presence of a catalyst suchas a chromium oxide.

According to the said document, the final selectivity towards F123 doesnot exceed 29%.

EP-B-407 990 proposes the chlorination of F133a to F123 by thermal orcatalytic activation, in the liquid phase under pressure. Theselectivity towards F123 may range from 67.9 to 83.4%, the reactionpressure ranging from 50 to 127 bar.

EP-A-402 874 proposes to react chlorine with F133a between 350 and 450°C., in the absence of a catalyst and of HF. According to the saiddocument, the production of F113a may be eliminated by means of aparticular combination of temperature conditions, contact time and molarratio of reagents.

U.S. Pat. No. 5,414,166 proposes a chlorination of F133a in the presenceof hydrogen, between 250 and 500° C. and preferably between 350 and 450°C.: the selectivity towards F123 may range from 65% to 92%.

U.S. Pat. No. 5,723,700 describes a step during which F133a, HF and Cl₂react, in the presence of a fluorination catalyst, between 300 and 450°C. to give essentially F134a and traces of F123.

DETAILED DESCRIPTION OF THE INVENTION

The aim of the invention is to propose a process for preparing F123 bychlorination of F133a, giving an improved conversion of F133a and/or animproved selectivity towards F123.

The aim of the invention is also to propose a process for preparing F123by chlorination of F133a, which may be carried out at a relativelymoderate temperature.

Another aim of the invention is to propose a process for preparing F123by chlorination of F133a, which may be carried out at atmosphericpressure or under moderate pressure, for example not exceeding 25 bar.

Another aim of the invention is to propose a process for preparing F123by chlorination of F133a, giving rise to a selectivity towards F123 ofgreater than 90%.

Another aim of the invention is to propose yet another such process,giving rise to a selectivity towards F123 of greater than 95%.

It has now been found that at least one of the abovementioned aims isachieved by means of the process described below.

One subject of the present invention is thus a process for preparing1,1,1-trifluoro-2,2-dichloroethane (F123) by placing1,1,1-trifluoro-2-chloroethane (F133a) in contact with chlorine, thesaid process being characterized in that the said placing in contact isperformed:

-   -   in the presence of HF;    -   under temperature conditions, with a contact time and with        Cl₂/F133a and HF/F133a molar ratios such that HF substantially        does not react with the F133a and the F123 formed, and promotes        the selectivity towards F123; and    -   in the presence of a bulk catalyst consisting of aluminum        fluoride or of a mixture of aluminum fluoride and alumina, or of        a catalyst based on iron, or on iron and nickel, supported on a        aluminum fluoride or on a mixture of aluminum fluoride and        alumina.

The invention relates more particularly to a process such that HF doesnot react substantially with F133a and F123 to give derivatives that aremore fluorinated than F133a, such as F124 or F134a.

In carrying out the process according to the invention, operatingconditions should be selected such that HF behaves essentially as adiluent and/or stabilizer for the reaction and the reagents, rather thanas a reagent in a fluorination reaction. In general, the temperatureconditions, the Cl₂/F133a and HF/F133a molar ratios and the contact timemay be chosen within known ranges for this type of chlorination reactionand, for example, as reported above with reference to the documentsrelating to the said chlorination reaction.

For purely illustrative purposes, which consequently cannot limit thefield of the invention, recommended orders of magnitude for theoperating conditions under consideration will be given below.

In general, the temperature of the reaction medium is between 150 and320° C. This temperature is preferably between 250 and 300° C.

The chlorine/F133a molar ratio may be between 0.01 and 0.50 and ispreferably between 0.1 and 0.3.

The HF/F133a molar ratio can generally be between 0.5 and 2.5. Forpractical reasons associated, inter alia, with the separation of theproducts for the purpose of recycling the unconsumed reagents, and theHF, a ratio of between 0.8 and 1.2 is preferably chosen.

The contact time between F133a, chlorine and HF on the catalyst may bebetween 5 and 100 seconds; it is recommended to have a contact time ofbetween 10 and 60 seconds. The contact time herein is calculated as theratio of the apparent volume of the catalyst to the total volume flowrate of gases fed into the reactor, under the reaction pressure andtemperature conditions.

The catalyst that may be used for this invention is a catalystconsisting of aluminum fluoride or a mixture of aluminum fluoride andalumina, onto which are optionally deposited oxides, halides and/oroxyhalides of iron, or else of iron and nickel. Catalysts consisting ofaluminum fluoride, alone or as a mixture with alumina, are describedespecially in EP 0 609 124. Catalysts based on iron, or on iron andnickel, are prepared by dry-impregnating aluminum fluoride or a mixtureof aluminum fluoride and alumina, either by a solution of ferricchloride, or by a solution containing a mixture of nickel chloride andferric chloride. The impregnation is followed by a step of drying undernitrogen.

When an iron-based catalyst is used, the iron content is generally lessthan 30% by weight and is preferably less than 15%. When a catalystbased on iron and nickel is used, the nickel content is less than 20% byweight and preferably less than 15%.

Prior to the chlorination reaction, the catalyst may be conditioned, ifnecessary, by a heat treatment in the presence of Cl₂ and/or HF, forexample according to the method described in EP-B-0 609 124.

As has been mentioned, the process in accordance with the inventionconsists especially in placing chlorine in contact with F133a, in thepresence of HF and a catalyst, under conditions such that HF does notsubstantially react with the F133a and the F123 formed to give morefluorinated derivatives. These conditions are advantageously chosenwithin the temperature, molar ratio and contact time zones indicatedpreviously, and it will fall to a person skilled in the art to selectthe exact conditions of a reaction, taking into account the desiredresult. Thus, once the temperature parameter has been chosen, forexample 280° C., it may be advantageous to reduce the Cl₂/F133a molarratio, for example to about 10% in order to obtain the best selectivitytowards 120 series at the expense of the 110 series. Similarly, for acertain temperature and a certain chlorine content, it will beconvenient to choose the contact time that makes it possible to combinea suitable degree of conversion of the F133a and a good selectivitytowards F123. Similarly also, the HF/F133a molar ratio may be chosen,for example, as a function of the desired or acceptable values for the110 series/120 series molar ratio. As mentioned, this HF/F133a ratio maygenerally range from 0.5 to 2.5 taking into account the other reactionconditions (temperature, contact time, Cl₂/F133a molar ratio), but,preferably, this HF/F133a molar ratio is in the region of 1, for examplebetween 0.8 and 1.2.

The preceding indications demonstrate that the values recommended forthe operating conditions have an essentially informative role, giventhat it would not constitute a departure from the context of theinvention to select, for any one of the reaction parameters, valueslying above or below the values indicated previously, provided that suchoperating modifications do not involve a reaction of HF with F133aleading to the formation of substantial amounts of more fluorinatedderivatives.

The chlorination reaction may be performed in the gas phase, in a fixedbed or in a fluid bed, batchwise or, preferably, continuously, with thepossibility of recycling the unconverted reagents and the HF into thereactor. The hydrochloric acid formed during the reaction is preferablyseparated out before recycling. The F123 recovered may be purified bydistillation according to the desired purity.

The chlorine may be introduced into the reactor in pure form or dilutedin an inert gas such as nitrogen. The materials used for theconstruction of the plant must be compatible with the presence ofchlorine and hydracids such as HCl and HF; they may be chosen, forexample, from “Hastelloy” or “Inconel” which are resistant to corrosivemedia containing these hydracids.

The chlorination reaction according to the invention may be performed atatmospheric pressure or at a pressure above atmospheric pressure. Forpractical reasons, the process is generally performed in a regionranging from 0 to 25 bar relative and preferably between 0 and 15 barrelative.

Under operating conditions liable to foul the catalyst, it may beprudent to introduce oxygen in low content with the reagents. Thiscontent may vary according to the operating conditions between 0.02% and5% relative to the organic reagents (molar percentage). The oxygen maybe introduced continuously or sequentially.

The process in accordance with the invention allows the preparation ofF123 from F133a, under moderate temperature and pressure conditions,with an excellent selectivity towards F123.

The starting 1,1,1-trifluoro-2-chloroethane (F133a) may itself beobtained by applying processes that are now well known. The F133a mayespecially be prepared by fluorinating trichloroethylene (for exampleaccording to the method recommended by McBee et al., Ind. Eng. Chem. 39,409-412), by fluorinating F132b, by fluorinating F130a, byhydrogenolysing F113a or by fluorinating F1122 (CF₂═CHCl).

In the invention, preference is given to F133a obtained by fluorinatingtrichloroethylene.

In this respect, a subject of the invention is also a process forpreparing F123 from trichloroethylene, the said process comprising:

-   -   a) a step of fluorinating trichloroethylene, in a reaction, in        the liquid phase or in the gas phase, in the presence of a        catalyst and at a pressure leading, after separating out HCl and        the heavy fractions, to a mixture of F133a accompanied by HF        entrained in azeotropic form;    -   b) a step of chlorinating F133a, by placing the said F133a in        contact with chlorine, in the presence of HF and a catalyst,        under temperature conditions, with a contact time and with        Cl₂/F133a and HF/F133a ratios such that HF does not        substantially react with the F133a and the F123 formed.

In phase a) for a liquid-phase process, a catalyst based on antimonysalts is preferably used and the process is advantageously performed ata pressure of at least 10 bar absolute. The trichloroethylene may alsobe reacted with HF in the presence of chromium oxide or chromiumoxyfluoride in a gas-phase process.

The F123 may be used in unmodified form, for example as a refrigerationpropellant and in the manufacture of foams, in which it advantageouslyreplaces F11 on account of its harmlessness with respect to the ozone inthe stratosphere. As a result, the process in accordance with theinvention, which, by virtue of the results it gives, may be exploitedindustrially, is particularly advantageous, starting either withtrichloroethylene or with F133a.

The F123 may also undergo additional fluorination and thus give F125(pentafluoroethane). This reaction may be performed according to variousprocesses that are now known: in general, this step involves placingF123 (alone or as a mixture with other compounds of the 120 series) incontact with HF in the presence of a fluorination catalyst to obtainF125.

This step may be performed in the vapour phase, and the catalyst may bechosen from the catalysts whose use is described, for example, inEP-B-609 124 or in the references quoted in the said patent, the saidpatent being incorporated herein especially for the conditionsrecommended for this reaction.

A subject of the invention is thus also a process for preparingpentafluoroethane (F125), the said process comprising:

-   -   a) a step of fluorinating trichloroethylene as described above        and resulting especially in F133a;    -   b) a step of chlorinating F133a, as described above and        resulting especially in F123;    -   c) a step of fluorinating F123, by placing F123 in contact with        HF, in the presence of a catalyst, with or without recycling of        F124, the fluorination of F124 possibly being the subject of a        separate step.

In this step, the catalyst is advantageously a mixed catalyst composedof oxides, halides and/or oxyhalides of nickel and of chromium asdescribed in EP-B-609 124. Catalysts based on chromium oxide oroxyfluoride or based on alumina or aluminum fluoride, optionally dopedwith a metal such as zinc, nickel or iron, may also be used. Suchcatalysts are described, for example, in EP-502 605 or WO 93/16798. Acatalyst of the chromium/charcoal type as described, for example, inEP-A-456 552 may also be used.

For this step, a mixed catalyst described above deposited on a supportconsisting of aluminum fluoride or a mixture of aluminum fluoride andalumina is preferably used.

The temperature of this fluorination reaction may be between 250 and470° C. and is preferably between 280 and 410° C. The contact timebetween HF and F123 may be between 3 and 100 s and preferably between 5and 30 s. The HF/F123 molar ratio may range from 1/1 to 20/1 andpreferably from 2/1 to 9/1.

Although the reaction may be performed at atmospheric pressure, it ispreferred to work under a slight pressure, for example not exceeding 10bar absolute, or even less than 5 bar absolute.

The F125 obtained may then be purified, for example by applying themethods described in FR-2 758 137 or WO 95/21147, the content of whichis incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

The process for preparing F125 from trichloroethylene, which alsoconstitutes a subject of the invention, may be carried out continuouslyin a plant as shown schematically by any one of the attached figures.

These figures illustrate an assembly scheme for the three Steps I, IIand III of the process under consideration.

The plant especially comprises (see FIG. 1):

Step I

-   -   a reactor (100) containing the catalyst;    -   inlets for trichloroethylene (101) and HF (102);    -   an HCl distillation column (103);    -   a column for separating out F133a+HF from the heavy fractions        (104):        Step II    -   a chlorination reactor (200) fed with:        -   F133a and HF (202);        -   chlorine (201);    -   an HCl separation column (203);    -   a column (204) for separating the crude F123 (206) from the        unreacted F133a (+especially azeotropic HF+unreacted Cl₂) which        are recycled (205);    -   a means for withdrawing the excess HF.        Step III    -   a fluorination reactor (300), fed with crude F123 (206/301)        originating from column (204) from the preceding step, with HF        (302) and optionally with crude F124 (310) recycled from column        (309);    -   at the outlet of reactor (300), the devices for processing the        reaction gases (columns 303, 304 and 305) intended to recover        the HCl formed as byproduct by the reaction and the unconverted        HF, and to neutralize the fluorocarbon compounds before        distilling them;    -   a column (306) for then extracting as the head fraction the F125        (307), the tail fraction (308) then being distilled off on the        column (309) to give a mixture F124+F123 (310) purified of its        content of heavy fractions, the said mixture then being recycled        into the reaction (300) to be fluorinated therein into F125.

An advantageous option of this scheme is represented in FIG. 2, in whichthere is a column (207) for purifying both the crude F123 (206) derivedfrom column (204) of Step II and the crude mixture F124+F123 derivedfrom the tail fraction of column (306) of Step III: in this option,which allows the reaction (300) to be fed with cleaner products, thecolumn (309) no longer needs to exist.

Needless to say, the industrial plant comprises additional devices thatare commonly used (purge, evaporators, superheater, decanters).

The invention also relates to a plant for producing F125 fromtrichloroethylene, and which comprises at least the succession ofdevices as represented in the figure.

EXAMPLES

The invention will now be illustrated by the following examples, whichare given purely for indicative purposes.

Example 1

Preparation of F123 by chlorination of F133a in the presence of HF andan iron-based catalyst.

75 cm³ of a catalyst based on iron deposited on fluoroalumina, having anFe content of 12% by weight, are introduced into an Inconel tube with aninside diameter of 21 mm.

The HF flow rate is adjusted to 0.91 mol/h and the temperature to 270°C. Next, a Cl₂/N₂ mixture containing 15 mol % of chlorine is introducedinto the reactor at a flow rate of 0.91 mol/h. Finally, CF₃—CH₂Cl isintroduced into the reactor at a flow rate of 0.90 mol/h and the totalreaction pressure is adjusted to 15 bar.

After reaction for 24 h, a gaseous sample is taken for analysis by gaschromatography. Another sample is taken after having removed the HF andchlorine from the flow derived from the reactor by sparging in washbottles with water and sodium hydroxide/sulphite and then after havingdried it over CaCl₂. It is similarly analysed by gas chromatography.

The conversion of F133a is 7.3% for a selectivity towards F123 of 96.9%.The 110 series/120 series ratio is 2.9%.

Examples 2 to 4

Preparation of F123 by chlorinating F133a in the presence of HF and aniron-based catalyst.

According to the same protocol as in Example 1, various conditions weretested. The test conditions and results obtained are collated in thetable below:

Conditions Example 2 Example 3 Example 4 Temperature (° C.) 270 280 280MR Cl₂/F133a 0.25 0.15 0.25 MR HF/F133a 1.1 1.1 1.2 Tc (s) 27 32 27Results Conversion F133a % 9.0 9.4 12.6 Selectivity towards 96.4 94.893.7 F123 % 110/120 series ratio % 3.4 3.9 5.7

Examples 5 to 7

Preparation of F123 by chlorinating F133a in the presence of HF andfluoroalumina as catalyst.

According to the same protocol as in Example 1, but replacing thecatalyst with a fluoroalumina, various conditions were tested.

The test conditions and results obtained are collated in the tablebelow:

Conditions Example 5 Example 6 Example 7 Temperature (° C.) 270 280 280MR Cl₂/F133a 0.23 0.18 0.27 MR HF/F133a 1.0 1.2 1.0 Tc (s) 26 35 29Results Conversion F133a % 7.9 10.2 11.9 Selectivity towards 98.4 95.996.4 F123 % 110/120 series ratio % 1.6 4.1 3.4

Example 8 Comparative

Preparation of F123 by chlorinating F133a in the presence offluoroalumina as catalyst and without HF.

75 cm³ of catalyst (fluoroalumina) are introduced into an Inconel tubewith an inside diameter of 21 mm. The catalyst is treated for 15 h with1 mol/h of anhydrous HF at 350° C. and atmospheric pressure.

Prior to the reaction, the HF flow is stopped, the temperature isreduced to 280° C. and a flow rate of nitrogen of 1.02 mol/h isintroduced into the reactor. Next, a Cl₂/N₂ mixture containing 15 mol %chlorine is introduced into the reactor at a flow rate of 1.02 mol/h.Finally, CF₃—CH₂Cl is introduced into the reactor at a flow rate of 1.1mol/h and the total reaction pressure is adjusted to 15 bar.

After reaction for 24 h, a gaseous sample is taken for analysis by gaschromatography. Another sample is taken after having removed the HF andchlorine from the flow derived from the reactor by sparging in washbottles containing water and sodium hydroxide/sulphite and then afterdrying it over CaCl₂. It is similarly analysed by gas chromatography.

The conversion of F133a is 9.5% for a selectivity towards F123 of 76.7%.The 110 series/120 series ratio is 23.5%.

Example 9 Comparative

Preparation of F123 by chlorinating F133a in the presence offluoroalumina as catalyst and without HF:

A test was performed according to the same protocol as in Example 9, butunder the following conditions: temperature=280° C., CL₂/F133a molarratio=0.27, N₂/F133a molar ratio=1, contact time=23 s.

The conversion of the F133a is then 17%, for a selectivity towards F123of 53%. The 110 series/120 series ratio is 70%.

Example 10 Comparative

Preparation of F123 by chlorinating F133a without HF and without acatalyst.

A flow rate of nitrogen of 0.94 mol/h is introduced into an emptyInconel tube with an inside diameter of 21 mm heated to 280° C., alongwith a Cl₂/N₂ mixture containing 15 mol % of chlorine at a flow rate of0.95 mol/h. Finally, CF₃—CH₂Cl is introduced into the reactor at a flowrate of 0.88 mol/h and the total reaction pressure is adjusted to 15bar.

After reaction for 24 h, a gaseous sample is taken for analysis by gaschromatography. Another sample is taken after having removed the HF andchlorine from the flow derived from the reactor by sparging in washbottles containing water and sodium hydroxide/sulphite and then afterhaving dried it over CaCl₂. It is similarly analysed by gaschromatography.

The conversion of the F133a is 2.5% for a selectivity towards F123 of91%.

The 110 series/120 series ratio is 8.5%.

Example 11 Comparative

Preparation of F123 by chlorinating F133a without HF and without acatalyst.

A test was performed according to the same protocol as in Example 15,but under the following conditions: temperature=280° C., Cl₂/F133a molarratio=0.25, N₂/F133a molar ratio=1, flow rate of F133a=0.93 mol/h.

The conversion of the F133a is then 2.8%, for a selectivity towards F123of 87%. The 110 series/120 series ratio is 13%.

Example 12 Comparative

Preparation of F123 by chlorinating F133a in the presence of HF and anNi—Cr catalyst supported on fluoroalumina.

75 cm³ of Ni—Cr catalyst supported on fluoroalumina, with an Ni contentof 6% by weight and a Cr content of 6% by weight (prepared as describedin patent FR 2 669 022), are introduced into an Inconel tube with aninside diameter of 21 mm. The catalyst is treated for 15 h with 1 mol/hof anhydrous HF at 350° C. and atmospheric pressure.

Prior to the reaction, the HF flow rate is adjusted to 1.2 mol/h and thetemperature to 280° C. Next, a Cl₂/N₂ mixture containing 15 mol % ofchlorine is introduced into the reactor at a flow rate of 1.56 mol/h.Finally, CF₃—CH₂Cl is introduced into the reactor at a flow rate of 1.18mol/h and the total reaction pressure is adjusted to 15 bar.

After reaction for 24 h, a gaseous sample is taken for analysis by gaschromatography. Another sample is taken after having removed the HF andchlorine from the flow derived from the reactor by sparging in washbottles containing water and sodium hydroxide/sulphite and then afterhaving dried it over CaCl₂. It is similarly analysed by gaschromatography.

The conversion of the F133a is 12.8% for a selectivity towards F123 of75.3%. The 110 series/120 series ratio is 8.2%.

Examples 13 and 14 Comparative

Preparation of F123 by chlorinating F133a in the presence of HF and anNi—Cr catalyst supported on fluoroalumina.

According to the same protocol as in Example 13, various conditions weretested. The results are given in the table below:

Conditions Example 13 Example 14 Temperature (° C.) 270 280 MR Cl₂/F133a0.28 0.28 MR HF/F133a 1.0 0.9 Tc (s) 32 31 Results Conversion F133a %16.9 21 Selectivity towards F123 % 73.7 74 110/120 series ratio % 13.112.9Although the invention has been described in conjunction with specificembodiments, it is evident that many alternatives and variations will beapparent to those skilled in the art in light of the foregoingdescription. Accordingly, the invention is intended to embrace all ofthe alternatives and variations that fall within the spirit and scope ofthe appended claims. The foregoing references are hereby incorporated byreference.

1. Process for preparing 1,1,1-trifluoro-2,2-dichloroethane (F123)comprising placing 1,1,1-trifluoro-2-chloroethane (F133a) in contactwith chlorine, said process being performed: in the presence of HF;under temperature conditions, with a contact time and with Cl₂/F133a andHF/F133a molar ratios wherein HF substantially does not react with theF133a and the F123 formed, and promotes selectivity towards F123; and inthe presence of a bulk catalyst consisting of aluminum fluoride or of amixture of aluminum fluoride and alumina, or of a catalyst based oniron, or on iron and nickel, supported on aluminum fluoride or on amixture of aluminum fluoride and alumina.
 2. Process according to claim1, wherein the temperature is between 150° C. and 320° C.
 3. Processaccording to claim 2, wherein the temperature is between 250° C. and300° C.
 4. Process according to claim 1, wherein the Cl₂/F133a molarratio is between 0.01 and 0.50.
 5. Process according to claim 4, whereinthe Cl₂/F133a molar ratio is between 0.1 and 0.3.
 6. Process accordingto claim 1, wherein the HF/F133a molar ratio is between 0.5 and 2.5. 7.Process according to claim 6, wherein the HF/F133a molar ratio isbetween 0.8 and 1.2.
 8. Process according to claim 1, wherein thecontact time between F133a, Cl₂ and HF on the catalyst is between 5 and100 seconds.
 9. Process according to claim 8, wherein the contact timeis between 10 and 60 seconds.
 10. Process according to claim 1, whereinthe catalyst is a bulk catalyst consisting of aluminum fluoride or amixture of aluminum fluoride and alumina.
 11. Process according to claim1, wherein the catalyst is a catalyst based on iron supported onaluminum fluoride or on a mixture of aluminum fluoride and alumina. 12.Process according to claim 11, in wherein the iron content is less than30% by weight.
 13. Process according to claim 1, wherein the catalyst isa catalyst based on iron and nickel supported on aluminum fluoride or ona mixture of aluminum fluoride and alumina.
 14. Process according toclaim 13, wherein the nickel content of the catalyst is less than 20% byweight.
 15. Process according to claim 1, wherein it is carried outcontinuously.
 16. Process according to claim 1, wherein the startingF133a is obtained by fluorination of trichloroethylene.
 17. Processaccording to claim 16, wherein the fluorination of trichloroethylene isperformed in the liquid phase under pressure, in the presence of acatalyst based on antimony salts or in the gaseous phase in the presenceof a catalyst based on chromium oxide or chromium oxyfluoride. 18.Process according to claim 12, wherein the iron content is less than15%.
 19. Process according to claim 11, wherein the catalyst is acatalyst based on iron and nickel supported on aluminum fluoride or on amixture of aluminum fluoride and alumina.
 20. Process according to claim12, wherein the catalyst is a catalyst based on iron and nickelsupported on aluminum fluoride or on a mixture of aluminum fluoride andalumina.
 21. Process according to claim 14, wherein the nickel contentis less than 15%.